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We report on the first observation of the organoxenon HXeCCH molecule in the gas phase. This molecule has been prepared in a molecular beam experiment by 193 nm photolysis of an acetylene molecule on Xen clusters (n≈390). Subsequently the molecule has been oriented via the pseudo-first-order Stark effect in a strong electric field of the polarized laser light combined with the weak electrostatic field in the extraction region of a time-of-flight spectrometer. The experimental evidence for the oriented molecule has been provided by measurements of its photodissociation. For comparison, photolysis of C2H2 on Arn clusters (n≈280) has been measured. Here the analogous rare gas molecule HArCCH could not be generated. The interpretation of our experimental findings has been supported by ab initio calculations. In addition, the experiment together with the calculations reveals information on the photochemistry of the HXeCCH molecule. The 193 nm radiation excites the molecule predominantly into the 2 1Σ+ state, which cannot dissociate the Xe–H bond directly, but the system evolves along the Xe–C coordinate to a conical intersection of a slightly nonlinear configuration with the dissociative 1 1Π state, which then dissociates the Xe–H bond. [ABSTRACT FROM AUTHOR]